CN-118125562-B - Preparation method and application of cathode material for electrocatalytic degradation of tetracycline

CN118125562BCN 118125562 BCN118125562 BCN 118125562BCN-118125562-B

Abstract

The invention belongs to the technical field of tetracycline degradation, discloses a preparation method and application of a cathode material for electrocatalytic degradation of tetracycline, and solves the technical problems of poor tetracycline degradation effect, short catalyst service life and difficult reuse of a powdery catalyst in the prior art. The preparation method of the cathode material for the electrocatalytically degraded tetracycline comprises the following steps of preparing a solution containing soluble nickel salt, soluble ferric salt and urea, filling the solution and a porous carrier into a reaction kettle for heat treatment, cleaning and drying the heat-treated porous carrier to obtain a precursor, and annealing the precursor to obtain the cathode material for the electrocatalytically degraded tetracycline. The preparation method of the cathode material for electrocatalytically degrading the tetracycline has the advantages of simple process, low cost, easy industrial production, convenient use, convenient regeneration and long service life, and can efficiently catalyze and activate PMS in an electrochemical environment, thereby improving the degradation efficiency of the tetracycline.

Inventors

GONG ZHENGJUN
ZHAO XIJIN
LV MIAO
ZHAO XILIN
WANG YUANYUAN
MENG FANQIANG
WANG DONGMEI
LI LINHU
Chen Lvcun

Assignees

西南交通大学
四川锦美环保股份有限公司

Dates

Publication Date: 20260512
Application Date: 20240119

Claims (9)

1. The preparation method of the cathode material for electrocatalytically degrading tetracycline is characterized by comprising the following steps of: Preparing a solution containing soluble nickel salt, soluble ferric salt and urea, wherein the molar ratio of nickel ions to iron ions to urea in the solution is1 (1-3) (12-16), the solvent of the solution contains 40-60% of ethylene glycol by volume percent, and the balance is deionized water; filling the solution and the porous carrier into a reaction kettle for heat treatment; washing and drying the heat-treated porous carrier to obtain a precursor; And (3) annealing the precursor to obtain the cathode material for electrocatalytically degrading the tetracycline.
2. The method for preparing the cathode material for the electrocatalytically degrading tetracycline as set forth in claim 1, wherein the porous carrier is a foam metal containing nickel and/or iron, and the foam metal is pretreated with hydrochloric acid and absolute ethyl alcohol.
3. The method for preparing the cathode material for the electrocatalytically degrading tetracycline according to claim 1, wherein the temperature of the heat treatment is 100-150 ℃ and the time is 6-14 hours.
4. The method for preparing the cathode material for the electrocatalytically degrading tetracycline according to claim 1, wherein the obtained cathode material for the electrocatalytically degrading tetracycline is regenerated by annealing, and/or the annealing treatment is carried out at a temperature of 250-400 ℃ for 1-3 hours.
5. A cathode material for electrocatalytically degrading tetracycline, which is characterized by being prepared by the preparation method of any one of claims 1-4.
6. The electrochemical catalytic degradation device for the tetracycline comprises an electrolytic cell and is characterized in that a cathode of the electrolytic cell is a cathode material for the electrochemical catalytic degradation of the tetracycline, which is prepared by the preparation method of claims 1-4.
7. The electrochemical catalytic degradation method of the tetracycline is characterized by comprising the step of carrying out electrochemical catalytic degradation treatment on a water body to be treated, which contains the tetracycline, the electrolyte and the oxidant, by adopting the electrochemical catalytic degradation equipment of claim 6.
8. The electrochemical catalytic degradation method of tetracycline as in claim 7, further comprising the steps of using a two-electrode single-chamber electrolytic cell, wherein the anode is a platinum electrode, the cathode is a cathode material for electrocatalytically degrading tetracycline, the oxidant is PMS, and the electrolyte is Na 2 SO 4 .
9. The electrochemical catalytic degradation method of tetracycline as set forth in claim 8, wherein the concentration of PMS in the water to be treated is 1-1.5 mM, the concentration of Na 2 SO 4 is 45-55 mM, the current density is 2-2.5 mA/cm 2 , and the electrolysis temperature is 25-40 ℃.

Description

Preparation method and application of cathode material for electrocatalytic degradation of tetracycline Technical Field The invention relates to the technical field of tetracycline degradation, in particular to a preparation method and application of a cathode material for electrocatalytically degrading tetracycline. Background Tetracyclines are one of the most widely used antibiotics worldwide, which can treat respiratory tract infections, urinary tract infections, venereal diseases, etc., and abuse of drugs and personal care products, etc., has led to tetracyclines being found in aquatic environments, foods and other samples, but if they remain in large amounts in aqueous environments, they can pose serious hazards to the ecological balance of the aqueous environment and human health, and thus it is very important to remove such antibiotics. Common removal methods include physical, chemical and biological methods such as ultrafiltration, activated carbon adsorption and microbiological treatment. However, these methods have problems of high cost, incomplete removal, secondary pollution, and the like. In recent years, advanced Oxidation Processes (AOPs) based on sulfate radicals (SO 4-) have received attention because of their high efficiency, safety, stable removal effect, wide application range and low cost. Compared with OH, SO 4- has longer half-life (30-40 μs), higher redox potential (2.6-3.1V) and wider pH application range (2-9). PMS is a major source of SO 4-, however PMS itself cannot degrade contaminants alone and needs to be activated to produce active species to degrade the contaminants. The main activation methods of PMS include catalysis, ultraviolet activation, thermal activation, ultrasonic activation, etc. Among them, the catalytic activation method is considered to be the most promising PMS activation method because of its high controllability, high efficiency, mild conditions, and easy operation. Currently, iron-based oxides with spinel structure exhibit significant catalytic capability during PMS activation. The spinel structure has octahedral or tetrahedral coordination, so that the spinel ferrite has stable crystal structure and can resist the influence of an acid-base environment and a redox environment in a certain range, and the spinel ferrite is a typical ferromagnetic material, can be adsorbed by a magnet in subsequent separation and recovery, and has high operation efficiency. However, due to the long reaction time, the activity is relatively low, so that the application of PMS activation to degrade tetracycline still cannot achieve the optimal degradation effect. Further, as the reaction proceeds, the high-valence metal on the catalyst surface is poor in reversibility to a low-valence state, resulting in loss of reactivity. For example, in iron-based oxides, the Fe (II) formation process is an energetically unfavorable redox cycle, which results in thermodynamically unfavorable regeneration of Fe (II) and poor recycling performance. In addition, the subsequent separation and recovery of the powdery iron-based oxide still has the problems of complex procedures and incomplete recovery, and also has the risk of secondary pollution. Disclosure of Invention The invention mainly aims to provide a preparation method of a cathode material for electrocatalytically degrading tetracycline, the cathode material for electrocatalytically degrading tetracycline, electrochemical catalytic degradation equipment for the tetracycline and an electrochemical catalytic degradation method for the tetracycline, so as to solve the technical problems of poor tetracycline degradation effect, short catalyst service life and difficult reuse of powdery catalysts in the prior art. In order to achieve the above purpose, the invention firstly provides a preparation method of a cathode material for electrocatalytically degrading tetracycline, which comprises the following technical scheme: the preparation method of the cathode material for electrocatalytically degrading tetracycline comprises the following steps: Preparing a solution containing a soluble nickel salt, a soluble iron salt and urea; filling the solution and the porous carrier into a reaction kettle for heat treatment; washing and drying the heat-treated porous carrier to obtain a precursor; And (3) annealing the precursor to obtain the cathode material for electrocatalytically degrading the tetracycline. As a further improvement of the preparation method of the cathode material for the electrocatalytically degrading tetracycline, the molar ratio of nickel ions to iron ions to urea in the solution is 1 (1-3): 12-16. As a further improvement of the preparation method of the cathode material for electrocatalytically degrading tetracycline, the solvent of the solution contains 40-60% of ethylene glycol by volume fraction, and the balance is deionized water. As a further improvement of the preparation method of the cathode material for the electrocataly